Preparation of single-helix carbon microcoils by catalytic CVD process

Three-dimensional (3D) single-helix spring-like carbon microcoils (SH-CMCs) were obtained by the catalytic pyrolysis of acetylene at 800-820 °C over the Fe-Ni alloy catalysts; their growth morphologies and microstructure were examined. The diameter of carbon fiber, from which the carbon nanocoils was formed, was about 0.5 μm, the coil diameter was about 1-2 μm, and the coil pitch was about the same with the coil diameter. The SH-CMCs were generally grown by a double-directional growth mode.     

Morphology and growth mechanism of single-helix spring-like carbon nanocoils with laces prepared using Ni/molecular sieve (Fe) catalyst

Single-helix spring-like carbon coils with laces grew over the Ni metal catalyst supported on molecular sieve containing a trace amount of an Fe impurity that originated from a kaolin clay raw material. The morphology, microstructure, and growth mechanism of the single-helix carbon nanocoils and laces were investigated. We found that a trace amount of Fe impurity contained in the molecular sieve was a key factor in the lace growth. It is considered that the Fe impurity may poison, restraint the formation of three crystal faces, resulting in the growth of single helix coils. It is also considered that a very strong inner stress is periodically formed between the boundary of two fibers, and the thin carbon film is swelled to form laces.     

Microwave absorption properties of carbon fibers with carbon coils of different morphologies (double microcoils and single nanocoils) grown on them

Double-carbon microcoils and single-carbon nanocoils were selectively grown on the surface of carbon fibers (CFs) via decomposition of acetylene at the temperature of 680 °C using Ni and Ni/Al₂O₃ catalysts, respectively. The morphology and microstructure of the as-prepared carbon coils–CFs were studied by SEM and Raman spectra, and the microwave absorption properties were also examined. Different from the double-carbon microcoils, no catalyst is observed at the growth tip of single-carbon nanocoils. It is considered that the Ni/Al₂O₃ binary catalysts would induce base growth model where only one remaining side of the catalyst particle contributes to nanofiber’s growth, resulting in the formation of single-carbon nanocoil. The single-carbon nanocoils–CFs composite shows lower complex permittivity, larger chirality admittance, as well as better microwave absorption properties than those of double-carbon microcoils–CFs. The maximum RL of the single-carbon nanocoils–CFs composite is ?41.2 dB, and the bandwidth of RL less than ?10 dB is up to 9.6 GHz, which are also better than those of other carbon nanomaterials in the literature.     

Preparation of carbon microcoils by catalytic methane hot-wire CVD process

Three-dimensional (3D) double-helix carbon microcoils (CMCs) were synthesized by the catalytic pyrolysis of methane using Ni catalyst in various hot-wire CVD processes. The most effective process is: using preheating method, in which methane was preheated at 1500 °C in a upper reaction tube by a hot wire, and chemical vapor deposition of carbon then occurred at 700-750 °C in a lower reaction tube, where CMCs were synthesized. The growth morphologies and microstructure were examined and compared with the conventional CMCs grown by acetylene catalytic pyrolysis.     

Synthesis and characterization of WS2 nanotube supported cobalt catalyst for hydrodesulfurization

WS₂ nanostructures hold structural characteristics which suggest they will be suitable for heterogeneous catalysis in the hydrodesulfurization (HDS) process. In this work, WS₂ nanotubes (INT-WS₂) were coated with cobalt nanoparticles using electroless plating method. Prior to cobalt deposition, the nanotubes surface was activated using palladium seeding process. The deposited cobalt nanoparticles had hcp crystal structure and formed non-uniform layer on the nanotubes surface. The catalytic reactivity of the produced cobalt coated nanotubes toward thiophene decomposition was characterized by an atmospheric flow reactor. The coated nanotubes revealed good catalytic reactivity toward thiophene mineralization. Further, the adsorption kinetics of thiophene on coated INT-WS₂ was studied by thermal desorption spectroscopy (TDS). The cobalt coated system was found to be more catalytically active than the pristine INT-WS₂ system. This result is promising since further optimization of the nanofabrication process of the catalyst should increase the conversion rates even further.     

Controllable synthesis of carbon microcoils/nanocoils by catalysts supported on ceramics using catalyzed chemical vapor deposition process

Carbon microcoils (CMCs) and carbon nanocoils (CNCs) were prepared by the catalytic pyrolysis of acetylene using Ni-based or Fe-based catalysts supported on molecular sieves by the catalyzed chemical vapor deposition (CCVD) process. The growth pattern, morphology and structure of the CMCs and CNCs (to be called by a joint name ‘carbon coils’) were examined in detail. By using a ceramic supporter, the anisotropy of the catalysts could be utilized and carbon coils could be more effectively obtained compared to non-supported alloy catalysts. Furthermore, the morphologies of the carbon coils could be controlled. The Raman spectra indicated that the structures of all these carbon coils were nanocrystalline phases in amorphous networks in spite of the different catalysts and preparation conditions.     

用SEM研究碳纤维的表面及断口形貌

采用SEM观察不同纺丝工艺的日本和国产碳纤维的表面及断口形貌,从结构上对比分析它们的差异,结果表明,表面缺陷减少,内部致密性提高,轴向微孔尺寸减小都是碳纤维强度提高的主要原因。国产干喷湿纺碳纤维表面缺陷和内部缺陷明显减少,有助于提高纤维拉伸强度。另外,洁净的生产环境及精细加工的设备有利于碳纤维缺陷的减少,使纤维拉伸强度提高的空间变大。     

Continuous synthesis of carbon nanotubes using a metal-free catalyst by CVD

This study demonstrates the first example of the use of a metal-free catalyst for the continuous synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD). In this paper silica nanoparticles produced from the thermal decomposition of PSS-(2-(trans-3,4-Cyclohexanediol)ethyl)-Heptaisobutyl substituted (POSS) were used as catalyst and ethanol was served as both the solvent and the carbon source for nanotube growth. The POSS/ethanol solution was nebulized by an ultrasonic beam. The tiny mists were continuously introduced into the CVD reactor for the growth of CNTs. The morphology and structure of the CNTs have been investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy. The obtained CNTs have a multi-walled structure with diameters mainly in the size range from 13 to 16 nm. Detailed investigations on the growth conditions indicate that the growth temperature and POSS concentration are important for achieving high-quality nanotubes, and that the existing of small amount of water in ethanol is effective to remove amorphous carbon species during the formation of CNTs. The mass production of CNTs without any metal contaminant will provide a chance for investing and understanding the intrinsic properties of CNTs and applications particularly in nanoelectronics and biomedicines.     

以LaNi5合金为催化剂制备碳纳米管的研究

在800℃下,以LaNi5合金粉末为催化剂,乙炔为原料,采用化学气相沉积法(CVD)分别在氢气氛和氮气氛下合成了多壁碳纳米管.研究了以LaNi5合金粉末为催化剂的条件下,反应气氛对生成碳纳米管的影响,探讨了CVD法生长碳纳米管的反应机理及LaNi5合金的催化机理.实验结果表明,反应过程中LaNi5分解为La3Ni7和Ni;在碳纳米管的生成过程中,La3Ni7进一步分解为La和Ni.氢的参与能显著改变生成的碳纳米管的质量.     

Growth of carbon nanostructures using a Pd-based catalyst

Carbon nanostructures were synthesized by decomposition of different carbon sources over an alumina supported palladium catalyst via Chemical Vapor Deposition (CVD). Several experimental conditions were varied to verify their influence in the synthesis products: temperature ramping rate, pre-annealing conditions, hydrogen pre-treatment, synthesis temperature and time, together with the use of different carbon sources. Depending on the experimental conditions carbon nanotubes and nanofibers with different shapes and structural characteristics were obtained. Straight, coiled and branched morphologies are the most common. Among our findings, the addition of hydrogen plays a significant role in the structure of the carbonaceous products. For example, the decomposition of acetylene on palladium catalysts at 800 degrees C in the absence of hydrogen produces only carbon micro- spheres as synthesis products. The incorporation of increasing amounts of hydrogen modifies the outcome, from thick fibers to carbon nanotubes. To verify the level of graphitization of the synthesis products we have used high resolution transmission electron microscopy (HRTEM) in addition to Raman spectroscopy. Our results, based on these complementary techniques, indicate the decomposition of acetylene on a palladium based catalyst, produces the best degree of graphitization in carbon nanotubes for a temperature of 800 degrees C and 100 cc/min of hydrogen flow. Similar hydrogen flows on the same catalyst, produced highly graphitized nanofibers by the decomposition of methane at 850 degrees C.     

The preparation of carbon nanotubes by dc arc discharge using a carbon cathode coated with catalyst

Carbon nanotubes (CNTs) were grown using a dc arc discharge process and relevant process parameters were investigated. Unlike the usual process in which a carbon anode is filled with metal catalyst powder, CNTs were prepared using a carbon cathode on which the metal catalyst had been deposited using an electroplating system. Various transition metals were investigated. The results show that multi walled carbon nanotubes (MWNTs) and single walled carbon nanotubes (SWNTs) can both be synthesized using this technique. SWNTs are detected in the soot sample collected around the cathode, whereas the MWNTs are detected mainly in the deposit sample collected from the central area of the cathode. The CNT yield varies depending on the catalyst used and the properties of a good catalyst are discussed.     

石墨化对微螺旋炭纤维热氧化动力学的影响

以乙炔为碳源,镍粉为催化剂,噻吩为助催化剂,采用化学气相沉积法制备微螺旋炭纤维;在氩气气氛中,2500℃下对所制微螺旋炭纤维进行石墨化处理.通过扫描电子显微镜观察微螺旋炭纤维的螺旋形貌和微观结构,用热重法研究微螺旋炭纤维的耐氧化性能,并探讨了微螺旋炭纤维的氧化动力学行为.结果表明:石墨化处理对微螺旋炭纤维具有显著的纯化作用,其螺旋形貌基本保持不变.微螺旋炭纤维的氧化反应较好地服从一级反应.微螺旋炭纤维石墨化前后的氧化反应活化能分别为263.004kJ/mol和297.191kJ/mol.石墨化处理明显提了微螺旋炭纤维的抗氧化性能.     

以氯化铁为前驱态催化剂制备碳纳米管

利用氯化铁为催化剂前驱体,结合悬浮催化剂法和基体法的优点,采用一种我们称之为悬浮-基体的新方法在700℃生长出了管壁清洁、直径均匀的碳纳米管,同时实验结果和分析证明,对所沉积的催化剂铁颗粒用氢气进行预处理具有细化碳纳米管和减少碳纳米管缺陷的作用。实验显示这种以氯化铁为催化剂前驱体的悬浮-基体法是一种很有前途实现碳纳米管廉价、大批量生产的方法。     

Multiwall and bamboo-like carbon nanotube growth by CVD using a semimetal as a catalyst

Multiwall carbon nanotubes have been synthesized on silicon substrates via atmospheric pressure chemical vapour deposition technique using bismuth as a catalyst. Field emission scanning electron microscopy analysis suggests that the samples grow through a tip growth mechanism. High-resolution transmission electron microscopy analysis shows spaghetti-like multiwall carbon nanotubes and with a bamboo-like structure obtained using the Bi catalyst. The quality, in terms of the graphitic crystallinity of the as grown carbon nanotubes, was analyzed by Raman analysis. The study shows that the catalyst, namely bismuth strongly influences the growth density and graphitic crystallinity of the grown carbon nanotubes.     

Growth of double-walled carbon nanotubes using a conditioning catalyst

Here we describe the effect of different synthetic conditions on the quality and purity of double-walled carbon nanotubes (DWNTs) with the aid of a conditioning catalyst. By lowering the reaction temperature down to 875 degrees C and utilizing a conditioning catalyst, increased purity and a decreased inner diameter of the DWNTs was achieved, while adverse results were observed with increasing reaction temperature. Based on detailed high-resolution transmission electron microscopy studies on the diameter distribution of the tubes, preferential growth conditions for DWNTs over single-wall carbon nanotubes are identified solely from increased carbon solubility considerations (caused by an increased portion of active carbon species by use of Mo) for the same distribution of metal particles.     

Influence of CVD conditions on the growth of carbon microcoils with circular cross-sections

The pyrolysis of C₂H₂ over a Ni powder catalyst in the atmosphere of H₂, H₂S and various inert gases was used to synthesize carbon microcoils (CMCs). The influences of the CVD conditions, esp. the gas flow rate of N₂, Ar, H₂O, or H₂ as well as reaction time on the growth of the CMCs, whose coiled fibers have circular cross-sections (circular CMCs), were investigated.     

Study on the synthesis of carbon fibers and CNF using potassium iodide catalyst

Most catalysts used in preparing carbon materials by chemical vapor deposition were transitional metals such as Fe, Co, Ni and only a few references were about the synthesis of carbon materials using water-soluble catalysts until now. Compared with metals, water-soluble catalysts can be conveniently removed from products. In our present works, water-soluble salt potassium iodide (KI) was found to be an efficient catalyst to grow carbon fibers and CNF under suitable conditions. Various structures of carbon fibers were synthesized by chemical vapor deposition using KI as the catalyst. And the experimental results showed that the nanostructure evolution of the fibers is strongly dependent on the temperature and history of the catalyst.     

Selective growth of carbon nanotubes using catalyst poisoning and geometric trench

This work suggests catalyst poisoning and geometric patterned approaches to selectively grow multiwall carbon nanotubes. Ferromagnetic particles as a catalyst for CNTs growth vanish when they are deposited over an aluminum thin film. Additionally, geometric features, such as trenches or cavities, are revealed to be capable of selectively ceasing the growth of CNTs even though catalytic thin films were covered on entire samples by an atmospheric thermal chemical vapor deposition technique.